Dye Sensitization - Grätzel cell

1. Sunlight energy (photon of light) passes through the titanium dioxide layer
and strikes electrons within the adsorbed dye molecules. Electrons gain this
energy and become excited because they have the extra energy.
2. The excited electrons escape the dye molecules and become free electrons.
These free electrons move through the titanium dioxide and accumulate at
the -ve plate (dyed TiO2 plate).
3. The free electrons then start to flow through the external circuit to produce
an electric current. This electric current powers the light bulb.
4. To complete the circuit, the dye is regenerated. The dye regains its lost
electrons from the iodide electrolyte. Iodide (I-) ions are oxidised (loss of 2
electrons) to tri-iodide (I3-). The free electrons on the graphite plate then
reduce the tri-iodide molecules back to their iodide state. The dye
molecules are then ready for the next excitation/oxid/red cycle. 1
 Photoelectrochemical processes in a dye-sensitized solar
cell.
Conducting
glass TiO2 Dye Electrolyte Cathode

Injection S*
-0.5
Maximum
Voltage
0 h
E vs 
NHE Red Mediator Ox
(V ) 0.5
Diffusion

1.0
+
S/S
e- e-

In a molecular system such as the dye, the gap between the highest
occupied molecular orbital and the lowest unoccupied level (HOMO-
LUMO gap) is analogous to the conduction band - valence band gap in a
semiconductor. 2
 The Grätzel Cell

Upper Plate :
Dye coated TiO2
Plate (-
Ve)

Lower Plate :
Graphite coated

conductor (+Ve)
By Hermetic sealing

Prepared Grätzel cell

3
4
Description of the Dye Sensitized Solar Cell:

Anode (conducting glass/TiO2/S //adsorbed + electrolyte-Redox // Metal (cathode,

Pt)
Under light (hv): (Energetic/ electron-transfer mechanism)

hv TiO2
So S* S+ + TiO2 (e-) (electron-transfer/injection step) on Anode

Red/Ox
S+ So (Regeneration Step) on Cathode

Thus e- flow through the circuit under the illumination  electrical energy
from solar energy

A small amount of Pt (5-10 µglcm2) is deposited to the counter-electrode to catalyze

the cathodic reduction of triiodide to iodide
5
 Construction of Grätzel cell
o In Grätzel cell a range of organic dyes are used.

o Examples: ruthenium-Polypyridine, Indoline dye & metal free organic dye.

o These dyes are extractable from simple foods such as hibiscus tea, tinned
summer fruits, blackberries.

Construction:
o Two transparent glass plates are perforated on one side with a transparent
thin layer of a conducting material.
o Onto the conducting sides, one plate is coated with graphite and the other
plate is coated with titanium dioxide (TiO2).
o A dye is then adsorbed onto the TiO2 layer by immersing the plate into a
dye solution of 10-4M in alcohol for 10 min. (approx.)
o The plates are then carefully sandwiched together and secured using a
paper clip.
o To complete the cell a drop of iodide electrolyte is added between the
plates.
o Figure shows a Grätzel cell prepared from hibiscus tea.
o The upper plate is the TiO2 plate, dyed with hibiscus tea and the lower plate
is coated with graphite.
6
 Working Principle of Grätzel Cell
o Sunlight energy passes through the titanium
dioxide layer and strikes electrons within the
adsorbed dye molecules.
o Electrons gain this energy and become excited
o The excited electrons escape from the dye
molecules to become free electrons.
o These free electrons move through theTiO2 and
accumulate at the –ve plate (dyed TiO2 plate).
o The free electrons then start to flow through the
external circuit to produce an electric current.
o This electric current powers the light bulb.
o To complete the circuit, the dye is regenerated.
o The dye regains its lost electrons from the iodide
electrolyte.
o Iodide (I-) ions are oxidised to tri-iodide (I3-).
o The free electrons at the graphite plate then reduce
the tri-iodide molecules back to their iodide state.
o The dye molecules are then ready for the next
excitation/oxidation/reduction cycle.
7
Ru 2,2-bipyridyle-4,4’-dicarboxylate and

cis-dithiocyanotobis(2,2’-bipyridyl-4,4’-dicarboxylate)-Ru(II) were

used and these can absorb solar light up to 650nm (1.9 eV) and 775

nm (1.6 eV), respectively.